Griffith Institute for Drug Discovery, Griffith University, Don Young Road, Nathan, QLD 4111, Australia.
Org Biomol Chem. 2018 Jan 3;16(2):256-261. doi: 10.1039/c7ob02123b.
A tetrahydropyranyl acetal bearing a proximal phenyl diazoketone substituent underwent Rh(ii)-catalysed C-H insertion via an 'anomalous' C-O bond-forming, rather than C-C bond-forming, transformation, giving spirocyclic orthoesters. Density functional theory calculations with M06 show that the formation of these anomalous products involves hydride transfer to the rhodium carbene, giving an intermediate zwitterion which undergoes C-O bond formation in preference to C-C bond formation.
带有近端苯基重氮酮取代基的四氢吡喃缩醛通过“异常”的 C-O 键形成而不是 C-C 键形成的转化，经历 Rh(ii)-催化的 C-H 插入，得到螺环原酸酯。用 M06 进行的密度泛函理论计算表明，这些异常产物的形成涉及氢化物转移到铑卡宾上，生成一个中间体两性离子，它优先进行 C-O 键形成而不是 C-C 键形成。
